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EP0991469B2 - Shaped body and method for the production thereof - Google Patents
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EP0991469B2 - Shaped body and method for the production thereof - Google Patents

Shaped body and method for the production thereof Download PDF

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Publication number
EP0991469B2
EP0991469B2 EP98933596A EP98933596A EP0991469B2 EP 0991469 B2 EP0991469 B2 EP 0991469B2 EP 98933596 A EP98933596 A EP 98933596A EP 98933596 A EP98933596 A EP 98933596A EP 0991469 B2 EP0991469 B2 EP 0991469B2
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EP
European Patent Office
Prior art keywords
mixture
molding
alcohol
titanium silicalite
titanium
Prior art date
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EP98933596A
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German (de)
French (fr)
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EP0991469B1 (en
EP0991469A1 (en
Inventor
Georg Heinrich Grosch
Ulrich Müller
Andreas Walch
Norbert Rieber
Wolfgang Harder
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BASF SE
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BASF SE
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00129—Extrudable mixtures

Definitions

  • the present invention relates to a titanium silicalite-containing molded body, a process for its preparation, and its use for the reaction of organic compounds, in particular for the epoxidation of organic compounds having at least one C-C double bond.
  • the molded article described herein has high abrasion resistance and excellent mechanical properties.
  • Abrasion-resistant shaped bodies of catalytically active compositions are used in many chemical processes, in particular in processes using a fixed bed. Accordingly, there is an immense wealth of literature on the subject. On the use of catalysts based on porous oxidic materials, such. Zeolites, and especially with respect to the deformation of such materials, there is significantly less literature.
  • the catalytically active material i. the porous oxidic material is added with a binder, an organic viscosity-increasing compound and a liquid for pasting the mass and compacted in a mixing or kneading apparatus or an extruder. Subsequently, the resulting plastic mass is deformed, in particular using an extruder or an extruder, and the resulting moldings dried and calcined.
  • hydrophilic polymers such as e.g. Cellulose or polyacrylates used.
  • DE-A 196 23 611.8 an oxidation catalyst with zeolite structure which has been formed by solidifying molding processes, and its use in the production of epoxides from olefins and hydrogen peroxide
  • DE-A 196 23 609.6 an oxidation catalyst based on titanium or vanadium silicalites with zeolite structure, which has also been shaped by solidifying molding processes and has a content of 0.01 to 30 wt .-% of one or more precious metals as defined therein.
  • EP-A 0 072 390 relates to a process for the production of compacts using pyrogenically prepared oxides.
  • Such pyrogenic oxides have a non-crystalline structure and are u. a. characterized in that they have no pores.
  • US Pat. No. 4,162,285 relates to the production of honeycomb-structured ceramics using as starting materials cordierite, mullite, aluminum oxide, zinc oxide, silicon nitride or a mixture of two or more thereof.
  • EP-A 0 639 404 relates to a process for preparing a catalyst, wherein the active catalyst component necessarily contains molybdenum and phosphorus.
  • porous oxide material-based molded article described above such as e.g.
  • zeolites, and in particular titanium silicalites have some disadvantages.
  • binders which could impart sufficient strength to such a shaped article, e.g. can not be used due to other negative properties.
  • binders which could impart sufficient strength to such a shaped article, e.g. can not be used due to other negative properties.
  • Aluminum-containing binders can not be used because of the increased acidity induced by the aluminum-containing binder resulting in increased ring opening and by-product formation.
  • titanium-containing binders can lead to high decomposition rates of the hydrogen peroxide used when these titanium-containing binders lead to detectable titanium dioxide contents in the molding.
  • binders which have a content of alkali metals or alkaline earth metals> 100 ppm.
  • the catalytic activity of e.g. Titanium silicalite are greatly impaired as the catalytically active Ti centers are inactivated by the alkali or alkaline earth metal ions.
  • an object of the present invention is to provide a titanium silicalite-containing Shaped body having sufficient mechanical stability to be used as a catalyst in a fixed bed.
  • the loss of activity or selectivity due to side reactions of the added binder should be avoided as compared to the prior art catalysts.
  • a method for its production is provided.
  • a molded article containing a titanium silicalite which has almost or no loss of activity and selectivity in its use as a catalyst can be obtained, provided that it comprises a mixture containing at least one alcohol and water as a pasting agent and a tetraalkoxysilane or a mixture of two or more thereof may be used as a binder.
  • the preparation according to the invention of the moldings described above starting from a titanium silicalite powder form involves the formation of a plastic mass comprising at least the titanium silicalite, a tetraalkoxysilane or a mixture of two or more thereof as a binder, a mixture containing at least one alcohol and water, an organic hydrophilic polymer or a mixture of two or more thereof as one or more organic viscosity-enhancing substances and other additives known in the art.
  • the plastic composition obtained by intimately mixing, especially kneading, the above components is preferably molded by extrusion or extrusion, and the resulting molded article is subsequently dried and finally calcined.
  • Zeolites are known to be crystalline aluminosilicates with ordered channel and cage structures having micropores.
  • micropores corresponds to the definition in "Pure Appl. Chem.” 45 , p. 71 ff., In particular p. 79 (1976), and designates pores having a pore diameter of less than 2 nm.
  • the network of such zeolites is composed of SiO 4 and AlO 4 tetrahedra which are linked by common oxygen bridges.
  • Titanium zeolites in particular those having an MFI-type crystal structure, as well as possibilities for their preparation, are described, for example, in EP-A 0 311 983 or EP-A 0 405 978.
  • silicon and titanium such materials may also contain additional elements such as Aluminum, zirconium, tin, iron, cobalt, nickel, gallium, boron or small amounts of fluorine.
  • the titanium thereof may be partially or completely replaced by vanadium, zirconium, chromium, niobium or iron.
  • the molar ratio of titanium and / or vanadium, zirconium, chromium, niobium or iron to the sum of silicon and titanium and / or vanadium, zirconium, chromium, niobium or iron is generally in the range from 0.01: 1 to 0, 1: 1.
  • Titanium zeolites with MFI structure are known to be identifiable by a particular pattern in determining their X-ray diffraction recordings and additionally by an Infrared (IR) scaffold vibration band at about 960 cm -1 and thus by alkali metal titanates or crystalline and amorphous TiO 2 Differentiate between phases.
  • IR Infrared
  • the said titanium, zirconium, chromium, niobium, iron and vanadium zeolites are thereby produced in that an aqueous mixture of an SiO 2 source, a titanium, zirconium, chromium, niobium, iron or vanadium source, for example titanium dioxide or a corresponding vanadium oxide, zirconium alcoholate, chromium oxide, niobium oxide or iron oxide and a nitrogen-containing organic base as a template (“stencil compound”), such as tetrapropylammonium hydroxide, optionally still with the addition of basic compounds, in a pressure vessel at elevated temperature over a period of several hours or a few days to form a crystalline product.
  • stencil compound such as tetrapropylammonium hydroxide
  • the titanium or the zirconium, chromium, niobium, iron and / or vanadium is at least partially present within the zeolite framework in varying proportions with 4-, 5- or 6-fold coordination.
  • a repeated washing treatment with sulfuric acid hydrogen peroxide solution may follow, after which the titanium or zirconium, chromium, niobium, iron, vanadium zeolite powder must be dried again and fired; This may be followed by treatment with alkali metal compounds to convert the zeolite from the H form to the cation form.
  • the titanium or zirconium, chromium, niobium, iron, vanadium zeolite powder thus prepared is then processed into a shaped body as described below.
  • Titanium silicalites are titanium zeolites with pentasil zeolite structure, in particular the types with X-ray mapping to the MFI, MEL or MFI / MEL mixed structure. Zeolites of this type are described, for example, in the reference to Meier and Olson cited above.
  • the shaped body according to the invention may comprise micropores, mesopores, macropores, micropores and mesopores, micropores and macropores or micropores, mesopores and macropores, the definition of the terms "mesopores” and "macropores” likewise being that of the abovementioned literature according to Pure Appl , Chem., And pores having a diameter of> 2 nm to about 50 nm or> 50 nm approximately.
  • Suitable binders are oxides of silicon.
  • a binder is silica, wherein the SiO 2 introduced in the form of tetraalkoxysilanes in the shaping step
  • a tetraalkoxysilane or a mixture of two or more thereof is added as a binder in step (I) of the process of the present invention.
  • tetraalkoxysilane be used as a binder.
  • Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane are to be mentioned in detail, with tetramethoxysilane and tetraethoxysilane being particularly preferred.
  • the shaped body according to the invention preferably contains up to about 80% by weight, more preferably about 1 to about 50% by weight and in particular about 3 to about 30% by weight of binder, in each case based on the total mass of the shaped body, wherein the content to binder from the amount of the resulting metal oxide results.
  • the tetraalkoxysilane used is used in such an amount that the resulting metal oxide content in the molded article about 1 to about 80 wt .-%, preferably about 2 to about 50 wt .-% and in particular about 3 to about 30 wt .-% , in each case based on the total mass of the molding.
  • a mixture containing at least one alcohol and water is used as pasting agent in the preparation of the shaped body according to the invention.
  • the alcohol content of this mixture is generally about 1 to about 80 wt .-%, preferably about 5 to about 70 wt .-% and in particular about 10 to about 60 wt .-%, each based on the total weight of the mixture.
  • the alcohol used is the alcohol component of the binder preferably However, it is not critical to use another alcohol.
  • organic viscosity-increasing substance organic hydrophilic polymers, e.g. Cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene, polytetrahydrofuran used.
  • organic hydrophilic polymers e.g. Cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene, polytetrahydrofuran used.
  • These substances primarily promote the formation of a plastic mass during the kneading, deformation and drying step by bridging the primary particles and, moreover, ensure the mechanical stability of the molding during deformation and drying.
  • amines or amine-like compounds e.g. Tetraalkylammonium compounds or amino alcohols
  • carbonate-containing substances such as calcium carbonate
  • Such other additives are described in EP-A 0 389 041, EP-A 0 200 260 and in WO 95/19222, which in this respect are fully incorporated by reference into the context of the present application.
  • acidic additives instead of basic additives, it is also possible to use acidic additives. Among other things, these can bring about a faster reaction of the metal acid ester with the porous oxidic material. Preference is given to organic acidic compounds which can be burned out by calcination after the deformation step. Particular preference is given to carboxylic acids. Of course, mixtures of two or more of the above additives can also be incorporated.
  • the order of addition of the constituents of the mass containing titanium silicalites is not critical. It is both possible first to add the binder, then to swap the organic viscosity-increasing substance, optionally the additive and finally the mixture containing at least one alcohol and water, as well as the order with respect to the binder, the organic viscosity-increasing substance and the additives.
  • the usually still powdery mass is homogenized in the kneader or extruder for 10 to 180 minutes. It is usually worked at temperatures in the range of about 10 ° C to the boiling point of the pasting agent and normal pressure or slight superatmospheric pressure. Thereafter, the addition of the remaining ingredients, and the resulting mixture is kneaded until a distensible or extrudable, plastic mass is formed.
  • extrusion takes place by extrusion in conventional extruders, for example into strands having a diameter of usually about 1 to about 10 mm, in particular about 2 to about 5 mm.
  • extrusion devices are described, for example, in Ullmanns Enzyklopädie der Technischen Chemie, 4th Edition, Vol. 2, p. 295 et seq., 1972.
  • extrusion press for deformation.
  • the resulting molded articles are dried at generally about 30 ° C to 140 ° C (1 to 20 hours, normal pressure) and calcined at about 400 ° C to about 800 ° C (3 to 10 hours, atmospheric pressure) ,
  • the strands or extrudates obtained can be comminuted. They are preferably comminuted into a granulate or chippings having a particle diameter of 0.1 to 5 mm, in particular 0.5 to 2 mm.
  • shaped bodies contain virtually no finer particles than those with about 0.1 mm minimum particle diameter.
  • the molded articles according to the invention or produced by the process according to the invention have a titanium silicalite-containing molding. - Compared with corresponding moldings of the prior art - an improved mechanical stability while maintaining the activity and selectivity.
  • the moldings according to the invention or produced according to the invention can be used for the catalytic conversion of organic molecules.
  • Reactions of this type are, for example, oxidations, the epoxidation of olefins such as the production of propylene oxide from propylene and H 2 O 2 , the hydroxylation of aromatics such as hydroquinone from phenol and H 2 O 2 , the conversion of alkanes to alcohols, aldehydes and Acids, isomerization reactions, such as the conversion of epoxides to aldehydes, and other in the literature with such moldings, in particular zeolite catalysts described reactions, as described for example in W.
  • the titanium silicalite discussed in detail above is particularly suitable for the epoxidation of olefins, preferably those having 2 to 8 C atoms, more preferably ethylene, propylene or butene, and in particular propene to the corresponding olefin oxides. Accordingly, the present invention particularly relates to the use of the molding described herein for the production of propylene oxide from propylene and hydrogen peroxide.
  • the present invention in its most general embodiment relates to the use of a mixture containing at least one alcohol and water as pasting agent, in combination with a tetraalkoxysilane as a binder for the preparation of deformable mixtures containing a Titansilikaliten.
  • the sealed autoclave (anchor agitator, 200 rpm) was brought to a reaction temperature of 175 ° C. After 92 hours, the reaction was complete. The cooled reaction mixture (white suspension) was removed by centrifuging and washed several times with water until neutral. The resulting solid was dried at 110 ° C within 24 hours (weight: 298 g). Subsequently, the template remaining in the zeolite was burnt off under air at 550 ° C in 5 hours. (Calcination loss: 14% by weight).
  • the pure white product had by wet chemical analysis a Ti content of 1.5 wt .-% and a content of residual alkali below 100 ppm.
  • the yield of SiO 2 used was 97%.
  • the crystallites had a size of 0.05 to 0.25 ⁇ m and the product showed a typical band at about 960 cm -1 in IR.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Adornments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

A process for the production of a molding containing at least one zeolite, wherein the at least one zeolite contains a titanium-, zirconium-, chromium-, niobium-, iron- or vanadium-containing zeolite:(I) adding a mixture consisting of at least one alcohol selected from the group consisting of methanol, ethanol, propanol or butanol, and water to a mixture containing said zeolite or a mixture of two or more thereof, and(II) kneading, molding, drying and calcining the mixture from (I);wherein the molding is useful as a catalyst, particularly in epoxidation reactions.

Description

Die vorliegende Erfindung betrifft einen einen Titansilikaliten enthaltenden Formkörper, ein Verfahren zu dessen Herstellung, sowie dessen Verwendung zur Umsetzung von organischen Verbindungen, insbesondere zur Epoxidation von organischen Verbindungen mit mindestens einer C-C-Doppelbindung. Der hierin beschriebene Formkörper weist hohe Abriebfestigkeit und ausgezeichnete mechanische Eigenschaften auf.The present invention relates to a titanium silicalite-containing molded body, a process for its preparation, and its use for the reaction of organic compounds, in particular for the epoxidation of organic compounds having at least one C-C double bond. The molded article described herein has high abrasion resistance and excellent mechanical properties.

Abriebfeste Formkörper aus katalytisch aktiven Massen werden in vielen chemischen Verfahren eingesetzt, insbesondere bei Verfahren unter Verwendung eines Festbetts. Demgemäß existiert eine immense Fülle von Literatur zu diesem Thema. Über den Einsatz von Katalysatoren auf der Basis poröser oxidischer Materialien, wie z.B. Zeolithe, und speziell bezüglich der Verformung derartiger Materialien existiert bedeutend weniger Literatur.Abrasion-resistant shaped bodies of catalytically active compositions are used in many chemical processes, in particular in processes using a fixed bed. Accordingly, there is an immense wealth of literature on the subject. On the use of catalysts based on porous oxidic materials, such. Zeolites, and especially with respect to the deformation of such materials, there is significantly less literature.

In der Regel wird zur Herstellung von Festkörpem die katalytisch aktive Masse, d.h. das poröse oxidische Material mit einem Bindemittel, einer organischen viskositätssteigernden Verbindung und einer Flüssigkeit zum Anteigen der Masse versetzt und in einer Misch- oder Knetvorrichtung oder einem Extruder verdichtet. Anschließend wird die daraus resultierende plastische Masse verformt, insbesondere unter Verwendung einer Strangpresse oder eines Extruders, und die resultierenden Formkörper getrocknet und calciniert.Typically, to produce solids, the catalytically active material, i. the porous oxidic material is added with a binder, an organic viscosity-increasing compound and a liquid for pasting the mass and compacted in a mixing or kneading apparatus or an extruder. Subsequently, the resulting plastic mass is deformed, in particular using an extruder or an extruder, and the resulting moldings dried and calcined.

Als Bindemittel werden dabei eine Reihe von anorganischen Verbindungen benutzt.As a binder while a number of inorganic compounds are used.

So wird gemäß der US-A 5,430,000 Titandioxid oder Titandioxidhydrat als Bindemittel verwendet. Als weitere, im Stand der Technik genannte Bindemittel sind zu nennen:

  • Aluminiumoxidhydrat oder andere aluminiumhaltige Bindemittel (WO 94/29408);
  • Gemische aus Silizium- und Aluminiumverbindungen (WO 94/13584);
  • Siliziumverbindungen (EP-A 0 592 050);
  • Tonmineralien (JP-A 03 037 156);
  • Alkoxysilane (EP-B 0 102 544).
Thus, according to US-A 5,430,000 titanium dioxide or titanium dioxide hydrate is used as a binder. Other binders mentioned in the prior art are:
  • Alumina hydrate or other aluminum-containing binders (WO 94/29408);
  • Mixtures of silicon and aluminum compounds (WO 94/13584);
  • Silicon compounds (EP-A 0 592 050);
  • Clay minerals (JP-A 03 037 156);
  • Alkoxysilanes (EP-B 0 102 544).

Als organische viskositätssteigernde Substanzen werden in der Regel hydrophile Polymere, wie z.B. Cellulose oder Polyacrylate, verwendet.As organic viscosity-increasing substances, hydrophilic polymers such as e.g. Cellulose or polyacrylates used.

Ferner beschreibt die Anmelderin selbst in der DE-A 196 23 611.8 einen Oxidationskatalysator mit Zeolith-Struktur, der durch verfestigende Formgebungsprozesse geformt worden ist, sowie dessen Verwendung bei der Herstellung von Epoxiden aus Olefinen und Wasserstoffperoxid, sowie, in der DE-A 196 23 609.6 einen Oxidationskatalysator auf der Basis von Titan- oder Vanadiumsilicaliten mit Zeolith-Struktur, der ebenfalls durch verfestigende Formgebungsprozesse geformt worden ist und einen Gehalt von 0,01 bis 30 Gew.-% an einem oder mehreren Edelmetallen, wie darin definiert, aufweist.Furthermore, the applicant himself describes in DE-A 196 23 611.8 an oxidation catalyst with zeolite structure which has been formed by solidifying molding processes, and its use in the production of epoxides from olefins and hydrogen peroxide, and, in DE-A 196 23 609.6 an oxidation catalyst based on titanium or vanadium silicalites with zeolite structure, which has also been shaped by solidifying molding processes and has a content of 0.01 to 30 wt .-% of one or more precious metals as defined therein.

In allen Druckschriften gemäß des oben zitierten Standes der Technik wird bei der Herstellung der dort beschriebenen Formkörper als Flüssigkeit zum Anteigen der Masse (Anteigungsmittel) Wasser verwendet.In all documents according to the above-cited prior art, water is used as a liquid for pasting the mass (pasting agent) in the production of the molded articles described therein.

Die EP-A 0 072 390 betrifft ein Verfahren zur Herstellung von Presslingen unter Verwendung von pyrogen hergestellten Oxiden. Derartige pyrogen hergestellte Oxide haben eine nicht-kristalline Struktur und zeichnen sich u. a. dadurch aus, daß sie keine Poren aufweisen.EP-A 0 072 390 relates to a process for the production of compacts using pyrogenically prepared oxides. Such pyrogenic oxides have a non-crystalline structure and are u. a. characterized in that they have no pores.

Die US 4 162 285 betrifft die Herstellung von Keramik mit Bienenwaben-Struktur, wobei als Edukte Cordierit, Mullit, Aluminiumoxid, Zinkoxid, Siliciumnitrid oder eine Mischung aus zwei oder mehr davon eingesetzt wird.US Pat. No. 4,162,285 relates to the production of honeycomb-structured ceramics using as starting materials cordierite, mullite, aluminum oxide, zinc oxide, silicon nitride or a mixture of two or more thereof.

Die EP-A 0 639 404 betrifft ein Verfahren zur Herstellung eines Katalysators, wobei die aktive Katalysatorkomponente zwingend Molybdän und Phosphor enthält.EP-A 0 639 404 relates to a process for preparing a catalyst, wherein the active catalyst component necessarily contains molybdenum and phosphorus.

Die oben beschriebenen auf einem porösen oxidischen Material basierenden Formkörper, wie z.B. Zeolithe und insbesondere Titansilicalite, besitzen jedoch einige Nachteile.The porous oxide material-based molded article described above, such as e.g. However, zeolites, and in particular titanium silicalites, have some disadvantages.

So besitzen viele der in der obigen Literatur beschriebenen Formkörper für eine Anwendung als Katalysator im Festbett nur eine unzureichende mechanische Festigkeit.Thus, many of the moldings described in the above literature for use as a catalyst in a fixed bed only inadequate mechanical strength.

Dies fällt insbesondere dann ins Gewicht, wenn Nebenreaktionen bestimmter Bindemittel unerwünscht sind und aus diesem Grund ganze Klassen von Bindemitteln, die einem derartigen Formkörper eine ausreichende Festigkeit verleihen könnten, z.B. aufgrund anderer negativer Eigenschaften nicht verwendet werden können. Beispielsweise können bei der Herstellung von Titansilicalit, der als Katalysator für die Epoxidation von z.B. Propylen mit Wasserstoffperoxid verwendet wird, aluminiumhaltige Bindemittel nicht verwendet werden, da es aufgrund der durch den aluminiumhaltigen Bindemittel induzierten Acidität zu vermehrter Ringöffnung und Nebenproduktbildung kommt. Darüber hinaus können Titan-haltige Bindemittel zu hohen Zersetzungsraten des eingesetzten Wasserstoffperoxids führen, wenn diese Titan-haltigen Bindemittel zu nachweisbaren Titandioxidgehalten im Formkörper führen.This is particularly important when side reactions of certain binders are undesirable and, for this reason, entire classes of binders which could impart sufficient strength to such a shaped article, e.g. can not be used due to other negative properties. For example, in the manufacture of titanium silicalite, used as a catalyst for the epoxidation of e.g. Aluminum-containing binders can not be used because of the increased acidity induced by the aluminum-containing binder resulting in increased ring opening and by-product formation. In addition, titanium-containing binders can lead to high decomposition rates of the hydrogen peroxide used when these titanium-containing binders lead to detectable titanium dioxide contents in the molding.

Ebenso unerwünscht ist es, Bindemittel zu verwenden, die einen Gehalt an Alkali- oder Erdalkalimetallen > 100 ppm besitzen. Durch Verwendung derartiger Bindemittel kann die katalytische Aktivität von z.B. Titansilicalit stark beeinträchtigt werden, da die katalytisch aktiven Ti-Zentren durch die Alkali- oder Erdalkaliionen inaktiviert werden.It is also undesirable to use binders which have a content of alkali metals or alkaline earth metals> 100 ppm. By using such binders, the catalytic activity of e.g. Titanium silicalite are greatly impaired as the catalytically active Ti centers are inactivated by the alkali or alkaline earth metal ions.

Somit liegt der vorliegenden Erfindung die Aufgabe zugrunde, einen einen Titansilikaliten enthaltenden Formkörper, der eine ausreichende mechanische Stabilität aufweist, um als Katalysator in einem Festbett verwendet zu werden, bereitzustellen. Bei dessen Verwendung für katalytische Reaktionen sollte die aufgrund von Nebenreaktionen des zugesetzten Bindemittels auftretenden Aktivitäts- oder Selektivitätseinbußen verglichen mit den Katalysatoren gemäß des Standes der Technik vermieden werden. Ferner wird ein Verfahren zu dessen Herstellung bereitgestellt.Thus, an object of the present invention is to provide a titanium silicalite-containing Shaped body having sufficient mechanical stability to be used as a catalyst in a fixed bed. When used for catalytic reactions, the loss of activity or selectivity due to side reactions of the added binder should be avoided as compared to the prior art catalysts. Furthermore, a method for its production is provided.

Überraschenderweise wurde gefunden, daß ein einen Titansilikaliten enthaltender Formkörper, der nahezu oder überhaupt keine Aktivitäts- und Selektivitätseinbußen bei seiner Verwendung als Katalysator aufweist, erhalten werden kann, sofern bei dessen Herstellung eine Mischung, enthaltend mindestens einen Alkohol und Wasser als Anteigungsmittel, und ein Tetraalkoxysilan oder ein Gemisch aus zwei oder mehr davon als Bindemittel verwendet werden.Surprisingly, it has been found that a molded article containing a titanium silicalite which has almost or no loss of activity and selectivity in its use as a catalyst can be obtained, provided that it comprises a mixture containing at least one alcohol and water as a pasting agent and a tetraalkoxysilane or a mixture of two or more thereof may be used as a binder.

Demgemäß betrifft die vorliegende Erfindung einen Titansilikaliten enthaltenden Formkörper, der erhältlich ist durch ein Verfahren, das die folgenden Stufen umfasst:

  • (I) Versetzen eines Gemischs, enthaltend einen Titansilikaliten und ein Tetraalkoxysilan oder ein Gemisch aus zwei oder mehr davon, mit einer Mischung, enthaltend mindestens einen Alkohol und Wasser,
  • (II) Kneten, Verformen, Trocknen und Calcinieren des gemäß Stufe (I) versetzten Gemischs,
wobei das Gemisch in Stufe (I) zusätzlich mit einem organischen hydrophilen Polymer oder einem Gemisch aus zwei oder mehr davon versetzt wird.
sowie ein Verfahren zur Herstellung eines mindestens einen Titansilikaliten enthaltenden Formkörpers, das die folgenden Stufen umfasst:
  • (I) Versetzen eines Gemischs, enthaltend einen Titansilikaliten und ein Tetraalkoxysilan oder ein Gemisch aus zwei oder mehr davon, mit einer Mischung, enthaltend mindestens einen Alkohol und Wasser.
  • (II) Kneten, Verformen, Trocknen und Calcinieren des gemäß Stufe (I) versetzten Gemischs,
wobei das Gemisch in Stufe (I) zusätzlich mit einem organischen hydrophilen Polymer oder einem Gemisch aus zwei oder mehr davon versetzt wird.Accordingly, the present invention relates to a titanium silicalite-containing molded article obtainable by a process comprising the following steps:
  • (I) adding a mixture containing a titanium silicalite and a tetraalkoxysilane or a mixture of two or more thereof with a mixture containing at least one alcohol and water,
  • (II) kneading, shaping, drying and calcining the mixture admixed according to step (I),
wherein the mixture in step (I) is additionally treated with an organic hydrophilic polymer or a mixture of two or more thereof.
and a process for producing a shaped body containing at least one titanium silicalite, comprising the following steps:
  • (I) adding a mixture containing a titanium silicalite and a tetraalkoxysilane or a mixture of two or more thereof with a mixture containing at least one alcohol and water.
  • (II) kneading, shaping, drying and calcining the mixture admixed according to step (I),
wherein the mixture in step (I) is additionally treated with an organic hydrophilic polymer or a mixture of two or more thereof.

Die erfindungsgemäße Herstellung der oben beschriebenen Formkörper ausgehend von einem Titansilikaliten Pulverform beinhaltet die Bildung einer plastischen Masse, die mindestens den Titansilikaliten, ein Tetraalkoxysilan oder ein Gemisch aus zwei oder mehr davon als Bindemittel, eine Mischung enthaltend mindestens einen Alkohol und Wasser, ein organisches hydrophiles Polymers oder ein Gemisch aus zwei oder mehr davon als eine oder mehrere organische viskositätssteigernde Substanzen und weitere aus dem Stand der Technik bekannte Zusatzstoffe enthält.The preparation according to the invention of the moldings described above starting from a titanium silicalite powder form involves the formation of a plastic mass comprising at least the titanium silicalite, a tetraalkoxysilane or a mixture of two or more thereof as a binder, a mixture containing at least one alcohol and water, an organic hydrophilic polymer or a mixture of two or more thereof as one or more organic viscosity-enhancing substances and other additives known in the art.

Die durch inniges Vermischen, insbesondere Kneten der obigen Komponenten erhaltene plastische Masse wird vorzugsweise durch Strangpressen oder Extrudieren verformt und der erhaltene Formkörper wird nachfolgend getrocknet und abschließend calciniert.The plastic composition obtained by intimately mixing, especially kneading, the above components is preferably molded by extrusion or extrusion, and the resulting molded article is subsequently dried and finally calcined.

Zeolithe sind bekanntermaßen kristalline Alumosilicate mit geordneten Kanal- und Käfigstrukturen, die Mikroporen aufweisen. Der Begriff "Mikroporen", wie er im Rahmen der vorliegenden Erfindung verwendet wird, entspricht der Definition in "Pure Appl. Chem." 45, S. 71 ff., insbesondere S. 79 (1976), und bezeichnet Poren mit einem Porendurchmesser von kleiner 2 nm. Das Netzwerk solcher Zeolithe ist aufgebaut aus SiO4- und AlO4-Tetraedern, die über gemeinsame Sauerstoffbrücken verbunden sind. Eine Übersicht der bekannten Strukturen findet sich beispielsweise bei W.M. Meier und D.H. Olson in "Atlas of Zeolithe Structure Types", Elsevier, 4. Auflage, London 1996.Zeolites are known to be crystalline aluminosilicates with ordered channel and cage structures having micropores. The term "micropores", as used in the context of the present invention, corresponds to the definition in "Pure Appl. Chem." 45 , p. 71 ff., In particular p. 79 (1976), and designates pores having a pore diameter of less than 2 nm. The network of such zeolites is composed of SiO 4 and AlO 4 tetrahedra which are linked by common oxygen bridges. An overview of the known structures can be found, for example, in WM Meier and DH Olson in "Atlas of Zeolite Structure Types", Elsevier, 4th edition, London 1996.

Ferner existieren Zeolithe, die kein Aluminium enthalten und bei denen im Silicatgitter anstelle des Si(IV) teilweise Titan als Ti(IV) vorhanden ist. Die Titanzeolithe, insbesondere solche mit einer Kristallstruktur vom MFI-Typ, sowie Möglichkeiten zu ihrer Herstellung sind beschrieben, beispielsweise in der EP-A 0 311 983 oder der EP-A 0 405 978. Außer Silizium und Titan können solche Materialien auch zusätzliche Elemente wie Aluminium, Zirkonium, Zinn, Eisen, Kobalt, Nickel, Gallium, Bor oder geringe Mengen an Fluor enthalten.Further, there are zeolites which do not contain aluminum and in which silicate lattice instead of Si (IV) partially contains titanium as Ti (IV). Titanium zeolites, in particular those having an MFI-type crystal structure, as well as possibilities for their preparation, are described, for example, in EP-A 0 311 983 or EP-A 0 405 978. In addition to silicon and titanium, such materials may also contain additional elements such as Aluminum, zirconium, tin, iron, cobalt, nickel, gallium, boron or small amounts of fluorine.

In den beschriebenen Zeolithen kann das Titan desselben teilweise oder vollständig durch Vanadium, Zirkonium, Chrom, Niob oder Eisen ersetzt sein. Das molare Verhältnis von Titan und/oder Vanadium, Zirkonium, Chrom, Niob oder Eisen zur Summe aus Silizium und Titan und/oder Vanadium, Zirkonium, Chrom, Niob oder Eisen liegt in der Regel im Bereich von 0,01:1 bis 0,1:1.In the described zeolites, the titanium thereof may be partially or completely replaced by vanadium, zirconium, chromium, niobium or iron. The molar ratio of titanium and / or vanadium, zirconium, chromium, niobium or iron to the sum of silicon and titanium and / or vanadium, zirconium, chromium, niobium or iron is generally in the range from 0.01: 1 to 0, 1: 1.

Titanzeolithe mit MFI-Struktur sind dafür bekannt, daß sie über ein bestimmtes Muster bei der Bestimmung ihrer Röntgenbeugungsaufnahmen sowie zusätzlich über eine Gerüstschwingungsbande im Infrarotbereich (IR) bei etwa 960 cm-1 identifiziert werden können und sich damit von Alkalimetalltitanaten oder kristallinen und amorphen TiO2-Phasen unterscheiden.Titanium zeolites with MFI structure are known to be identifiable by a particular pattern in determining their X-ray diffraction recordings and additionally by an Infrared (IR) scaffold vibration band at about 960 cm -1 and thus by alkali metal titanates or crystalline and amorphous TiO 2 Differentiate between phases.

Üblicherweise stellt man die genannten Titan-, Zirkonium-, Chrom-, Niob-, Eisen- und Vanadiumzeolithe dadurch her, daß man eine wäßrige Mischung aus einer SiO2-Quelle, einer Titan-, Zirkonium-, Chrom-, Niob-, Eisen bzw. Vanadium-Quelle, wie z.B. Titandioxid bzw. einem entsprechenden Vanadiumoxid, Zirkoniumalkoholat, Chromoxid, Nioboxid oder Eisenoxid und einer stickstoffhaltigen organischen Base als Templat ("Schablonen-Verbindung"), wie z.B. Tetrapropylammoniumhydroxid, gegebenenfalls noch unter Hinzufügen von basischen Verbindungen, in einem Druckbehälter unter erhöhter Temperatur im Zeitraum mehrerer Stunden oder einiger Tage umsetzt, wobei ein kristallines Produkt entsteht. Dieses wird abfiltriert, gewaschen, getrocknet und zur Entfernung der organischen Stickstoffbase bei erhöhter Temperatur gebrannt. In dem so erhaltenen Pulver liegt das Titan, bzw. das Zirkonium, Chrom, Niob, Eisen und/oder Vanadium zumindest teilweise innerhalb des Zeolithgerüsts in wechselndem Anteil mit 4-, 5- oder 6-facher Koordination vor. Zur Verbesserung der katalytischen Verhalens kann sich noch eine mehrmalige Waschbehandlung mit schwefelsaurer Wasserstoffperoxidlösung anschließen, worauf das Titan- bzw. Zirkonium-, Chrom-, Niob-, Eisen-, Vanadiumzeolith-Puiver erneut getrocknet und gebrannt werden muß; daran kann sich eine Behandlung mit Alkalimetallverbindungen anschließen, um den Zeolith von der H-Form in die Kation-Form zu überführen. Das so hergestellte Titan- bzw. Zirkonium-, Chrom-, Niob-, Eisen-, Vanadiumzeolith-Pulver wird dann, wie nachstehend beschrieben, zu einem Formkörper verarbeitet.Usually, the said titanium, zirconium, chromium, niobium, iron and vanadium zeolites are thereby produced in that an aqueous mixture of an SiO 2 source, a titanium, zirconium, chromium, niobium, iron or vanadium source, for example titanium dioxide or a corresponding vanadium oxide, zirconium alcoholate, chromium oxide, niobium oxide or iron oxide and a nitrogen-containing organic base as a template ("stencil compound"), such as tetrapropylammonium hydroxide, optionally still with the addition of basic compounds, in a pressure vessel at elevated temperature over a period of several hours or a few days to form a crystalline product. This is filtered off, washed, dried and fired at elevated temperature to remove the organic nitrogen base. In the powder thus obtained, the titanium or the zirconium, chromium, niobium, iron and / or vanadium is at least partially present within the zeolite framework in varying proportions with 4-, 5- or 6-fold coordination. To improve the catalytic behavior, a repeated washing treatment with sulfuric acid hydrogen peroxide solution may follow, after which the titanium or zirconium, chromium, niobium, iron, vanadium zeolite powder must be dried again and fired; This may be followed by treatment with alkali metal compounds to convert the zeolite from the H form to the cation form. The titanium or zirconium, chromium, niobium, iron, vanadium zeolite powder thus prepared is then processed into a shaped body as described below.

Titansilikalite sind Titan zeolithe mit Pentasil-Zeolith-Struktur, insbesondere die Typen mit röntgenographischer Zuordnung zur MFI-, MEL- oder MFI/MEL-Mischstruktur. Zeolithe dieses Typs sind beispielsweise in der oben angegebenen Literaturstelle von Meier und Olson beschrieben.Titanium silicalites are titanium zeolites with pentasil zeolite structure, in particular the types with X-ray mapping to the MFI, MEL or MFI / MEL mixed structure. Zeolites of this type are described, for example, in the reference to Meier and Olson cited above.

Auch bezüglich der Porenstruktur der erfindungsgemäßen Formkörper existieren keine besonderen Beschränkungen, d.h. der erfindungsgemäße Formkörper kann Mikroporen, Mesoporen, Makroporen, Mikro- und Mesoporen, Mikro- und Makroporen oder Mikro-, Meso- und Makroporen aufweisen, wobei die Definition der Begriffe "Mesoporen" und "Makroporen" ebenfalls derjenigen in oben erwähnter Literatur gemäß Pure Appl. Chem. entspricht und Poren mit einem Durchmesser von > 2 nm bis ca. 50 nm bzw. > ungefähr 50 nm bezeichnet.Also with respect to the pore structure of the molded articles of the invention, there are no particular limitations, i. E. The shaped body according to the invention may comprise micropores, mesopores, macropores, micropores and mesopores, micropores and macropores or micropores, mesopores and macropores, the definition of the terms "mesopores" and "macropores" likewise being that of the abovementioned literature according to Pure Appl , Chem., And pores having a diameter of> 2 nm to about 50 nm or> 50 nm approximately.

Als Bindemittel eignen sich Oxide des Siliziums. Von besonderem Interesse als Bindemittel ist Siliziumdioxid, wobei das SiO2 in Form von Tetraalkoxysilanen in den Formgebungsschritt eingebrachtSuitable binders are oxides of silicon. Of particular interest as a binder is silica, wherein the SiO 2 introduced in the form of tetraalkoxysilanes in the shaping step

Als Bindemittel wird ein Tetraalkoxysilan oder ein Gemisch aus zwei oder mehr davon als Bindemittel in Stufe (I) des erfindungsgemäßen Verfahrens zugesetzt.As a binder, a tetraalkoxysilane or a mixture of two or more thereof is added as a binder in step (I) of the process of the present invention.

Im Rahmen der vorliegenden Erfindung werden Tetraalkoxysilan als Bindemittel verwendet. Im einzelnen zu nennen sind dabei Tetramethoxysilan, Tetraethoxysilan, Tetrapropoxysilan und Tetrabutoxysilan, wobei Tetramethoxysilan und Tetraethoxysilan besonders bevorzugt sind.In the context of the present invention tetraalkoxysilane be used as a binder. Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane are to be mentioned in detail, with tetramethoxysilane and tetraethoxysilane being particularly preferred.

Der erfindungsgemäße Formkörper enthält vorzugsweise bis zu ungefähr 80 Gew.-%, weiter bevorzugt ungefähr 1 bis ungefähr 50 Gew.-% und insbesondere ungefähr 3 bis ungefähr 30 Gew.-% Bindemittel, jeweils bezogen auf die Gesamtmasse des Formkörpers, wobei sich der Gehalt an Bindemittel aus der Menge des entstehenden Metalloxids ergibt.The shaped body according to the invention preferably contains up to about 80% by weight, more preferably about 1 to about 50% by weight and in particular about 3 to about 30% by weight of binder, in each case based on the total mass of the shaped body, wherein the content to binder from the amount of the resulting metal oxide results.

Das verwendete Tetraalkoxysilan wird in einer solchen Menge eingesetzt, daß der daraus entstehende Metalloxid-Gehalt im Formkörper ungefähr 1 bis ungefähr 80 Gew.-%, vorzugsweise ungefähr 2 bis ungefähr 50 Gew.-% und insbesondere ungefähr 3 bis ungefähr 30 Gew.-%, jeweils bezogen auf die Gesamtmasse des Formkörpers liegt.The tetraalkoxysilane used is used in such an amount that the resulting metal oxide content in the molded article about 1 to about 80 wt .-%, preferably about 2 to about 50 wt .-% and in particular about 3 to about 30 wt .-% , in each case based on the total mass of the molding.

Wie sich aus obigem bereits ergibt, können selbstverständlich auch Gemische aus zwei oder mehr der oben genannten Bindemittel eingesetzt werden.As is clear from the above, of course, mixtures of two or more of the above-mentioned binders can be used.

Essentiell für die vorliegende Erfindung ist es, daß bei der Herstellung des erfindungsgemäßen Formkörpers als Anteigungsmittel eine Mischung enthaltend mindestens einen Alkohol und Wassers verwendet wird. Dabei beträgt der Alkoholgehalt dieser Mischung im allgemeinen ungefähr 1 bis ungefähr 80 Gew.-%, vorzugsweise ungefähr 5 bis ungefähr 70 Gew.-% und insbesondere ungefähr 10 bis ungefähr 60 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Mischung.It is essential for the present invention that a mixture containing at least one alcohol and water is used as pasting agent in the preparation of the shaped body according to the invention. The alcohol content of this mixture is generally about 1 to about 80 wt .-%, preferably about 5 to about 70 wt .-% and in particular about 10 to about 60 wt .-%, each based on the total weight of the mixture.

Vorzugsweise entspricht der verwendete Alkohol der Alkoholkomponente des als Bindemittel vorzugsweise verwendeten Metallsäureesters, wobei es jedoch auch nicht kritisch ist, einen anderen Alkohol zu verwenden.Preferably, the alcohol used is the alcohol component of the binder preferably However, it is not critical to use another alcohol.

Bezüglich der verwendbaren Alkohole bestehen keinerlei Beschränkungen, sofern sie wassermischbar sind. Es können demnach sowohl Monoalkohole mit 1 bis 4 C-Atomen und wassermischbare mehrwertige Alkohole verwendet werden. Insbesondere werden Methanol, Ethanol, Propanol sowie n-, iso-, tert.-Butanol, sowie Gemische aus zwei oder mehr davon verwendet.With respect to the usable alcohols, there are no restrictions, as long as they are water-miscible. Accordingly, it is possible to use both monoalcohols having 1 to 4 C atoms and water-miscible polyhydric alcohols. In particular, methanol, ethanol, propanol and n-, iso-, tert-butanol, as well as mixtures of two or more thereof are used.

Als organische viskositätssteigernde Substanz werden organische hydrophile Polymere, wie z.B. Cellulose, Stärke, Polyacrylate, Polymethacrylate, Polyvinylalkohol, Polyvinylpyrrolidon, Polyisobuten, Polytetrahydrofuran verwendet. Diese Substanzen fördern in erster Linie die Bildung einer plastischen Masse während des Knet-, Verformungs- und Trocknungsschritts durch Verbrücken der Primärpartikel und gewährleisten darüber hinaus die mechanische Stabilität des Formkörpers beim Verformen und Trocknen. Diese Substanzen werden beim Calcinieren wieder aus dem Formkörper entfernt.As the organic viscosity-increasing substance, organic hydrophilic polymers, e.g. Cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene, polytetrahydrofuran used. These substances primarily promote the formation of a plastic mass during the kneading, deformation and drying step by bridging the primary particles and, moreover, ensure the mechanical stability of the molding during deformation and drying. These substances are removed during calcination again from the molding.

Als weitere Zusatzstoffe können Amine oder aminartige Verbindungen, wie z.B. Tetraalkylammoniumverbindungen oder Aminoalkohole, sowie carbonathaltige Substanzen, wie z.B. Calciumcarbonat, zugesetzt werden. Derartige weitere Zusatzstoffe sind in EP-A 0 389 041, EP-A 0 200 260 und in WO 95/19222 beschrieben, die diesbezüglich vollumfänglich in den Kontext der vorliegenden Anmeldung durch Bezugnahme einbezogen werden.As further additives, amines or amine-like compounds, e.g. Tetraalkylammonium compounds or amino alcohols, as well as carbonate-containing substances, such. Calcium carbonate can be added. Such other additives are described in EP-A 0 389 041, EP-A 0 200 260 and in WO 95/19222, which in this respect are fully incorporated by reference into the context of the present application.

Statt basischer Zusatzstoffe ist es auch möglich saure Zusatzstoffe zu verwenden. Diese können unter anderem eine schnellere Reaktion des Metallsäureesters mit dem porösen oxidischen Material bewirken. Bevorzugt sind organische saure Verbindungen, die sich nach dem Verformungsschritt durch Calcinieren herausbrennen lassen. Besonders bevorzugt sind Carbonsäuren. Selbstverständlich können auch Gemische aus zwei oder mehr der oben genannten Zusatzstoffe eingebaut werden.Instead of basic additives, it is also possible to use acidic additives. Among other things, these can bring about a faster reaction of the metal acid ester with the porous oxidic material. Preference is given to organic acidic compounds which can be burned out by calcination after the deformation step. Particular preference is given to carboxylic acids. Of course, mixtures of two or more of the above additives can also be incorporated.

Die Zugabereihenfolge der Bestandteile der den Titansilikaliten enthaltenden Masse ist nicht kritisch. Es ist sowohl möglich, zuerst das Bindemittel zuzugeben, anschließend die organische viskositätssteigernde Substanz, ggf. den Zusatzstoff und zum Schluß die Mischung enthaltend mindestens einen Alkohol und Wassers, als auch die Reihenfolge bezüglich des Bindemittels, der organischen viskositätssteigernden Substanz und der Zusatzstoffe zu vertauschen.The order of addition of the constituents of the mass containing titanium silicalites is not critical. It is both possible first to add the binder, then to swap the organic viscosity-increasing substance, optionally the additive and finally the mixture containing at least one alcohol and water, as well as the order with respect to the binder, the organic viscosity-increasing substance and the additives.

Nach der Zugabe des Bindemittels zum pulverförmigen Titansilikaliten dem gegebenenfalls die organische viskositätssteigernde Substanz bereits zugegeben worden ist, wird die in der Regel noch pulverförmige Masse 10 bis 180 Minuten im Kneter oder Extruderhomogenisiert. Dabei wird in der Regel bei Temperaturen im Bereich von ungefähr 10 °C bis zum Siedepunkt des Anteigungsmittel und Normaldruck oder leichtem überathmosphärischem Druck gearbeitet. Danach erfolgt die Zugabe der restlichen Bestandteile, und das so erhaltene Gemisch wird solange geknetet, bis eine verstrangbare oder extrudierfähige, plastische Masse entstanden ist.After the addition of the binder to the powdered titanium silicalite to which optionally the organic viscosity-increasing substance has already been added, the usually still powdery mass is homogenized in the kneader or extruder for 10 to 180 minutes. It is usually worked at temperatures in the range of about 10 ° C to the boiling point of the pasting agent and normal pressure or slight superatmospheric pressure. Thereafter, the addition of the remaining ingredients, and the resulting mixture is kneaded until a distensible or extrudable, plastic mass is formed.

Prinzipiell können für die Knetung und die Verformung alle herkömmlichen Knet- und Verformungsvorrichtungen bzw. Verfahren, wie sie zahlreich aus dem Stand der Technik bekannt sind und für die Herstellung von z.B. Katalysator-Formkörpern allgemein verwendet werden.In principle, all conventional kneading and shaping devices or methods, as are well known in the art and used for the production of e.g. Catalyst moldings are generally used.

Wie bereits angedeutet, sind jedoch Verfahren bevorzugt, bei denen die Verformung durch Extrusion in üblichen Extrudern, beispielsweise zu Strängen mit einem Durchmesser von üblicherweise ungefähr 1 bis ungefähr 10 mm, insbesondere ungefähr 2 bis ungefähr 5 mm, erfolgt. Derartige Extrusionsvorrichtungen werden beispielsweise in Ullmanns Enzyklopädie der Technischen Chemie, 4. Auflage, Bd. 2, S. 295 ff., 1972 beschrieben. Neben der Verwendung eines Extruders wird ebenfalls vorzugsweise eine Strangpresse zur Verformung verwendet.As already indicated, however, processes are preferred in which the extrusion takes place by extrusion in conventional extruders, for example into strands having a diameter of usually about 1 to about 10 mm, in particular about 2 to about 5 mm. Such extrusion devices are described, for example, in Ullmanns Enzyklopädie der Technischen Chemie, 4th Edition, Vol. 2, p. 295 et seq., 1972. Besides the use of an extruder, it is also preferable to use an extrusion press for deformation.

Nach Beendigung des Strangpressens oder Extrudierens werden die erhaltenen Formkörper bei im allgemeinen ungefähr 30 °C bis 140 °C (1 bis 20 h, Normaldruck) getrocknet und bei ungefähr 400 °C bis ungefähr 800 °C (3 bis 10 h, Normaldruck) calciniert.After completion of extrusion or extrusion, the resulting molded articles are dried at generally about 30 ° C to 140 ° C (1 to 20 hours, normal pressure) and calcined at about 400 ° C to about 800 ° C (3 to 10 hours, atmospheric pressure) ,

Selbstverständlich können die erhaltenen Stränge bzw. Extrudate zerkleinert werden. Sie werden dabei vorzugsweise zu einem Granulat oder Splitt mit einem Partikeldurchmesservon 0,1 bis 5 mm, insbesondere 0,5 bis 2 mm zerkleinert.Of course, the strands or extrudates obtained can be comminuted. They are preferably comminuted into a granulate or chippings having a particle diameter of 0.1 to 5 mm, in particular 0.5 to 2 mm.

Dieses Granulat oder dieser Splitt und auch auf anderem Wege erzeugte Formkörper enthalten praktisch keine feinkörnigeren Anteile als solche mit ungefähr 0,1 mm Mindestpartikeldurchmesser.These granules or chippings and also produced by other means shaped bodies contain virtually no finer particles than those with about 0.1 mm minimum particle diameter.

Die erfindungsgemäßen bzw nach dem erfindungsgemäßen Verfahren hergestellten, einen Titansilikaliten enthaltenden Formkörper besitzen . - verglichen mit entsprechenden Formkörpern des Standes der Technik - eine verbesserte mechanische Stabilität bei gleichzeitigem Erhalt der Aktivität und Selektivität.The molded articles according to the invention or produced by the process according to the invention have a titanium silicalite-containing molding. - Compared with corresponding moldings of the prior art - an improved mechanical stability while maintaining the activity and selectivity.

Die erfindungsgemäßen bzw. erfindungsgemäß hergestellten Formkörper können zur katalytischen Umwandlung organischer Moleküle eingesetzt werden. Umsetzungen dieser Art sind beispielsweise Oxidationen, die Epoxidation von Olefinen wie z.B. die Herstellung von Propylenoxid aus Propylen und H2O2, die Hydroxylierung von Aromaten, wie z.B. Hydrochinon aus Phenol und H2O2, die Umwandlung von Alkanen zu Alkoholen, Aldehyden und Säuren, Isomerisierungsreaktionen, wie z.B. die Umwandlung von Epoxiden zu Aldehyden, sowie weitere in der Literatur mit derartigen Formkörpern, insbesondere Zeolith-Katalysatoren beschriebenen Umsetzungen, wie sie beispielsweise in W. Hölderich, "Zeolites: Catalysts for the Synthesis of Organic Compounds", Elsevier, Stud. Surf. Sci. Catal., 49, Amsterdam (1989), S. 69 bis 93, und insbesondere für mögliche Oxidationsreaktionen von B. Notari in Stud. Surf. Sci. Catal., 37 (1987), S. 413 bis 425, beschrieben sind.The moldings according to the invention or produced according to the invention can be used for the catalytic conversion of organic molecules. Reactions of this type are, for example, oxidations, the epoxidation of olefins such as the production of propylene oxide from propylene and H 2 O 2 , the hydroxylation of aromatics such as hydroquinone from phenol and H 2 O 2 , the conversion of alkanes to alcohols, aldehydes and Acids, isomerization reactions, such as the conversion of epoxides to aldehydes, and other in the literature with such moldings, in particular zeolite catalysts described reactions, as described for example in W. Hölderich, "Zeolites: Catalysts for the Synthesis of Organic Compounds", Elsevier , Stud. Surf. Sci. Catal., 49 , Amsterdam (1989), pp. 69-93, and in particular for possible oxidation reactions of B. Notari in Stud. Surf. Sci. Catal., 37 (1987), pp. 413 to 425.

Dabei eignet sich der vorstehend ausführlich diskutierte Titansilikalit insbesondere für die Epoxidation von Olefinen, vorzugsweise solchen mit 2 bis 8 C-Atomen, weiter bevorzugt Ethylen, Propylen oder Buten, und insbesondere Propen zu den entsprechenden Olefinoxiden. Demgemäß betrifft die vorliegende Erfindung insbesondere die Verwendung des hierin beschriebenen Formkörpers zur Herstellung von Propylenoxid ausgehend von Propylen und Wasserstoffperoxid.The titanium silicalite discussed in detail above is particularly suitable for the epoxidation of olefins, preferably those having 2 to 8 C atoms, more preferably ethylene, propylene or butene, and in particular propene to the corresponding olefin oxides. Accordingly, the present invention particularly relates to the use of the molding described herein for the production of propylene oxide from propylene and hydrogen peroxide.

Darüber hinaus betrifft die vorliegende Erfindung in ihrer allgemeinsten Ausgestaltungsform die Verwendung einer Mischung enthaltend mindestens einen Alkohol und Wasser als Anteigungsmittel, in Kombination mit einem Tetraalkoxysilan als Bindemittel zur Herstellung verformbarer Gemische, die einen Titansilikaliten enthalten.Moreover, the present invention in its most general embodiment relates to the use of a mixture containing at least one alcohol and water as pasting agent, in combination with a tetraalkoxysilane as a binder for the preparation of deformable mixtures containing a Titansilikaliten.

BEISPIELEEXAMPLES Beispiel 1example 1

In einem Vierhalskolben (4 l Inhalt) wurden 910 g Tetraethylorthosilicat vorgelegt und aus einem Tropftrichter innerhalb von 30 min mit 15 g Tetraisopropylorthotitanat unter Rühren (250 U/min, Blattrührer) versetzt. Es bildete sich eine farblose, klare Mischung. Anschließend versetzte man mit 1600 g einer 20 gew.-%igen Tetrapropylammoniumhydroxid-Lösung (Alkaligehalt < 10 ppm) und rührte noch eine Stunde nach. Bei 90 °C bis 100 °C wurde das aus der Hydrolyse gebildete Alkoholgemisch (ca. 900 g) abdestilliert. Man füllte mit 3 I Wasser auf und gab das mittlerweile leicht opaque Sol in einen 5 l fassenden Rührautoklaven aus Edelstahl.910 g of tetraethyl orthosilicate were placed in a four-necked flask (4 l capacity) and 15 g of tetraisopropyl orthotitanate were added from a dropping funnel over the course of 30 minutes with stirring (250 rpm, paddle stirrer). It formed a colorless, clear mixture. Subsequently, 1600 g of a 20% strength by weight tetrapropylammonium hydroxide solution (alkali content <10 ppm) were added and stirring was continued for one hour. At 90 ° C to 100 ° C, the alcohol mixture formed from the hydrolysis (about 900 g) was distilled off. It was filled with 3 l of water and gave the now slightly opaque sol in a 5 l stirred autoclave made of stainless steel.

Mit einer Heizrate von 3 °C/min wurde der verschlossene Autoklav (Ankerrührer, 200 U/min) auf eine Reaktionstemperatur von 175 °C gebracht. Nach 92 Stunden war die Reaktion beendet. Das erkaltete Reaktionsgemisch (weiße Suspension) wurde abzentrifugiert und mehrfach mit Wasser neutral gewaschen. Der erhaltene Feststoff wurde bei 110 °C innerhalb von 24 Stunden getrocknet (Auswaage: 298 g). Anschließend wurde unter Luft bei 550 °C in 5 Stunden das im Zeolithen verbliebene Templat abgebrannt. (Calcinierungsverlust: 14 Gew.-%).At a heating rate of 3 ° C / min, the sealed autoclave (anchor agitator, 200 rpm) was brought to a reaction temperature of 175 ° C. After 92 hours, the reaction was complete. The cooled reaction mixture (white suspension) was removed by centrifuging and washed several times with water until neutral. The resulting solid was dried at 110 ° C within 24 hours (weight: 298 g). Subsequently, the template remaining in the zeolite was burnt off under air at 550 ° C in 5 hours. (Calcination loss: 14% by weight).

Das reinweiße Produkt hatte nach naßchemischer Analyse einen Ti-Gehält von 1,5 Gew.-% und einen Gehalt an Restalkali unterhalb 100 ppm. Die Ausbeute auf eingesetztes SiO2 betrug 97 %. Die Kristallite hatten eine Größe von 0,05 bis 0,25 µm und das Produkt zeigte im IR eine typische Bande bei ca. 960 cm-1.The pure white product had by wet chemical analysis a Ti content of 1.5 wt .-% and a content of residual alkali below 100 ppm. The yield of SiO 2 used was 97%. The crystallites had a size of 0.05 to 0.25 μm and the product showed a typical band at about 960 cm -1 in IR.

Beispiel 2Example 2

120 g Titansilicalit-Pulver, synthetisiert gemäß Beispiel 1, wurden mit 48 g Tetramethoxysilan 2 h lang im Kneter vermischt. Anschließend wurden 6 g Walocel (Methylcellulose) zugegeben. Zum Anteigen gab man nun 77 ml einer Wasser-Methanol-Mischung mit einem Methanolgehalt von 25 Gew.-% zu. Die erhaltene Masse wurde weitere 2 h im Kneter verdichtet und dann in einer Strangpresse zu 2 mm-Strängen verformt. Die erhaltenen Stränge wurden bei 120 °C 16 h lang getrocknet und dann bei 500 °C 5 h lang calciniert. Die so erhaltenen Formkörper wurden auf ihre Seitendruckfestigkeit geprüft. Die Seitendruckfestigkeit betrug 4,11 kg.10 g der so erhaltenen Formkörper wurden zu Splitt (Partikelgröße 1 - 2 mm) verarbeitet und als Katalysator A in der Epoxidation von Propen mit Wasserstoffperoxid verwendet.120 g of titanium silicalite powder, synthesized according to Example 1, were mixed with 48 g of tetramethoxysilane for 2 hours in a kneader. Subsequently, 6 g Walocel (methyl cellulose) were added. For pasting was now added 77 ml of a water-methanol mixture with a methanol content of 25 wt .-% to. The mass obtained was compacted for a further 2 hours in a kneader and then molded in an extruder into 2 mm extrudates. The resulting strands were dried at 120 ° C for 16 hours and then calcined at 500 ° C for 5 hours. The moldings thus obtained were tested for lateral compressive strength. The side crushing strength was 4.11 kg. 10 g of the resulting molded articles were processed into chippings (particle size 1 - 2 mm) and used as catalyst A in the epoxidation of propene with hydrogen peroxide.

Vergleichsbeispiel 1Comparative Example 1

120 g Titansilicalit-Pulver, synthetisiert gemäß Beispiel 1, wurden mit 48 g Tetramethoxysilan 2 h lang im Knetervermischt. Anschließend wurden 6 g Walocel (Methylcellulose) zugegeben. Zum Anteigen gab man nun 80 ml Wasser zu. Die erhaltene Masse wurde weitere 2 h im Kneter verdichtet und dann in einer Strangpresse zu 2 mm-Strängen verformt. Die erhaltenen Stränge wurden bei 120 °C 16 h lang getrocknet und dann bei 500 °C 5 h lang calciniert. Die so erhaltenen Formkörperwurden auf ihre Seitendruckfestigkeit geprüft. Die Seitendruckfestigkeit betrug 3,59 kg. 10 g der so erhaltenen Formkörper wurden zu Splitt (Partikelgröße 1 - 2 mm) verarbeitet und als Katalysator B in der Epoxidation von Propen mit Wasserstoffperoxid verwendet.120 g of titanium silicalite powder synthesized according to Example 1 were mixed in the kneader with 48 g of tetramethoxysilane for 2 hours. Subsequently, 6 g Walocel (methyl cellulose) were added. For pasting it was now added to 80 ml of water. The mass obtained was compacted for a further 2 hours in a kneader and then molded in an extruder into 2 mm extrudates. The resulting strands were dried at 120 ° C for 16 hours and then calcined at 500 ° C for 5 hours. The molded articles thus obtained were tested for lateral pressure resistance. The lateral crushing strength was 3.59 kg. 10 g of the moldings thus obtained were processed into chips (particle size 1 - 2 mm) and used as catalyst B in the epoxidation of propene with hydrogen peroxide.

Beispiel 3Example 3

120 g Titansilicalit-Pulver, synthetisiert gemäß Beispiel 1, wurden trocken mit 6 g Walocel (Methylcellulose) gemischt und mit 48 g Tetraethoxysilan 30 min im Kneter vermischt. Zum Anteigen gab man nun 75 ml einer Wasser-Ethanol-Mischung mit einem Ethanolgehalt von 50 Gew-% zu. Die so erhaltene Masse wurde 1 h lang im Kneter verdichtet und dann in einer Strangpresse zu 2 mm-Strängen verformt. Die so erhaltenen Stränge wurden bei 120 °C 16 h lang getrocknet und dann bei 500 °C 5 h lang calciniert. Die so erhaltenen Formkörper wurden auf ihre Seitendruckfestigkeit geprüft. Die Seitendruckfestigkeit betrug 3,08 kg. 10 g der so erhaltenen Formkörper wurden zu Splitt (Partikelgröße 1 - 2 mm) verarbeitet und als Katalysator C in der Epoxidation von Propen mit Wasserstoffperoxid verwendet.120 g of titanium silicalite powder, synthesized according to Example 1, were mixed dry with 6 g of Walocel (methylcellulose) and mixed with 48 g of tetraethoxysilane for 30 minutes in a kneader. For the pasting, 75 ml of a water-ethanol mixture with an ethanol content of 50% by weight were added. The mass thus obtained was compacted for 1 hour in the kneader and then molded in an extruder to 2 mm extrudates. The strands thus obtained were at 120 ° C Dried for 16 h and then calcined at 500 ° C for 5 h. The moldings thus obtained were tested for lateral compressive strength. The lateral crushing strength was 3.08 kg. 10 g of the moldings thus obtained were processed into chips (particle size 1 - 2 mm) and used as catalyst C in the epoxidation of propene with hydrogen peroxide.

Vergleichsbeispiel 2Comparative Example 2

120 g Titansilicalit-Pulver, synthetisiert gemäß Beispiel 1, wurden mit 48 g Tetraethoxysilan 2 h im Kneter vermischt. Anschließend wurden 6 g Walocel (Methylcellulose) zugegeben. Zum Anteigen gab man nun 79 ml Wasser zu. Die so erhaltene Masse wurde 1 h lang im Kneter verdichtet und dann in einer Strangpresse zu 2 mm-Strängen verformt. Die erhaltenen Stränge wurden bei 120 °C 16 h lang getrocknet und dann bei 500 °C 5 h lang calciniert. Die so erhaltenen Formkörper wurden auf ihre Seitendruckfestigkeit geprüft. Die Seitendruckfestigkeit betrug 1,92 kg. 10 g der so erhaltenen Formkörper wurde zu Splitt (Partikelgröße 1 - 2 mm) verarbeitet und als Katalysator D in der Epoxidation von Propen mit Wasserstoffperoxid verwendet.120 g of titanium silicalite powder, synthesized according to Example 1, were mixed with 48 g of tetraethoxysilane for 2 h in a kneader. Subsequently, 6 g Walocel (methyl cellulose) were added. To prepare it was now added to 79 ml of water. The mass thus obtained was compacted for 1 hour in the kneader and then molded in an extruder to 2 mm extrudates. The resulting strands were dried at 120 ° C for 16 hours and then calcined at 500 ° C for 5 hours. The moldings thus obtained were tested for lateral compressive strength. The lateral crushing strength was 1.92 kg. 10 g of the shaped bodies thus obtained were processed into chips (particle size 1 - 2 mm) and used as catalyst D in the epoxidation of propene with hydrogen peroxide.

Vergleichsbeispiel 3Comparative Example 3

120 g Titansilicalit-Pulver, synthetisiert gemäß Beispiel 1, wurden mit 6 g Walocel (Methylcellulose), 30 g Kieselsol (Ludox AS-40) und 85 ml Wasser 2 h im Kneter verdichtet. Die so erhaltene Masse wurde dann in einer Strangpresse zu
2 mm-Strängen verformt. Die erhaltenen Stränge wurden bei 120 °C 16 h lang getrocknet und dann bei 500 °C 5 h lang calciniert. Die so erhaltenen Formkörper wurden auf ihre Seitendruckfestigkeit geprüft. Die Seitendruckfestigkeit betrug 0,89 kg. 10 g der so erhaltenen Formkörper wurden zu Splitt (Partikelgröße 1 - 2 mm) verarbeitet und als Katalysator E in der Epoxidation von Propen mit Wasserstoffperoxid verwendet.120 g of titanium silicalite powder, synthesized according to Example 1, were compacted in the kneader with 6 g of Walocel (methylcellulose), 30 g of silica sol (Ludox AS-40) and 85 ml of water for 2 hours. The mass thus obtained was then added in an extruder
2 mm strands deformed. The resulting strands were dried at 120 ° C for 16 hours and then calcined at 500 ° C for 5 hours. The moldings thus obtained were tested for lateral compressive strength. The lateral crushing strength was 0.89 kg. 10 g of the resulting shaped articles were processed into chips (particle size 1 - 2 mm) and used as catalyst E in the epoxidation of propene with hydrogen peroxide.

Beispiele 4 bis 8Examples 4 to 8

In einen Stahlautoklaven mit Korbeinsatz und Begasungsrührerwurden jeweils soviel Gramm an Katalysator A bis E eingebaut, daß die Masse an eingebautem Titansilicalit 0,5 g betrug. Der Autoklav wurde mit 100 g Methanol befüllt, verschlossen und auf seine Dichtigkeit überprüft. Anschließend wurde er auf 40 °C temperiert und 11 g flüssiges Propen in den Autoklaven dosiert. Nun wurden mittels einer HPLC-Pumpe 9,0 g einer wäßrigen Wasserstoffperoxidlösung (Gehalt an Wasserstoffperoxid in der Lösung 30 Gew.-%) in den Autoklaven gepumpt und die Wasserstoffperoxidreste in den Zuleitungen anschließend mit 16 ml Methanol in den Autoklaven gespült. Der Anfangsgehalt der Reaktionslösung an Wasserstoffperoxid betrug 2,5 Gew- %. Nach 2 h Reaktionszeit wurde der Autoklav abgekühlt und entspannt. Der flüssige Austrag wurde cerimetrisch auf Wasserstoffperoxid untersucht. Die Analyse und die Bestimmung des Gehalts an Propylenoxid erfolgte gaschromatographisch. Katalysator Gehalt an Propylenoxid (Gew.-%) Restgehalt an Wasserstoffperoxid (Gew.-%) A 1,42 0,99 B (Vergleich) 1,19 1,12 C 1,28 1,10 D (Vergleich) 1,15 1,20 E (Vergleich) 1,49 0,98 Into a steel autoclave with basket insert and a gassing stirrer were incorporated in each case so many grams of catalyst A to E that the mass of incorporated titanium silicalite was 0.5 g. The autoclave was filled with 100 g of methanol, sealed and checked for leaks. It was then heated to 40 ° C and dosed 11 g of liquid propene in the autoclave. 9.0 g of an aqueous hydrogen peroxide solution (content of hydrogen peroxide in the solution 30% by weight) were then pumped into the autoclave by means of an HPLC pump and the hydrogen peroxide residues in the feed lines were subsequently rinsed into the autoclave with 16 ml of methanol. The initial content of the reaction solution of hydrogen peroxide was 2.5% by weight. After a reaction time of 2 hours, the autoclave was cooled and vented. The liquid effluent was examined cerimetrically for hydrogen peroxide. The analysis and the determination of the content of propylene oxide was carried out by gas chromatography. catalyst Content of propylene oxide (wt%) Residual content of hydrogen peroxide (wt .-%) A 1.42 0.99 B (comparison) 1.19 1.12 C 1.28 1.10 D (comparison) 1.15 1.20 E (comparison) 1.49 0.98

Aus den Beispielen ist ersichtlich, daß durch die erfindungsgemäße Verwendung von Tetraalkoxysilanen als Bindemittel und Wasser-Alkoholmischungen als Anteigungsmittel eine erhöhte Seitendruckfestigkeit bei gleichzeitigem Erhalt der Selektivität und Aktivität erhalten werden kann.It can be seen from the examples that the use according to the invention of tetraalkoxysilanes as binders and water-alcohol mixtures as pasting agents allows an increased lateral compressive strength to be obtained while at the same time maintaining selectivity and activity.

Claims (8)

  1. A molding containing a titanium silicalite and obtainable by a process which comprises the following stages:
    (I) addition of a mixture containing at least one alcohol and water to a mixture containing a titanium silicalite and a tetraalkoxysilane or a mixture of two or more thereof, and
    (II) kneading, molding, drying and calcination of the mixture according to stage (I) after addition,
    wherein an organic hydrophilic polymer or a mixture of two or more thereof is additionally added to the mixture in stage (I).
  2. A process for the production of a molding containing at least one titanium silicalite, which comprises the following stages:
    (I) addition of a mixture containing at least one alcohol and water to a mixture containing a titanium silicalite and a tetraalkoxysilane or a mixture of two or more thereof, and
    (II) kneading, molding, drying and calcination of the mixture according to stage (I) after addition,
    wherein an organic hydrophilic polymer or a mixture of two or more thereof is additionally added to the mixture in stage (I).
  3. A process as claimed in claim 2, wherein the alcohol in the mixture containing at least one alcohol and water corresponds to the alcohol in the tetraalkoxysilane.
  4. A process as claimed in claim 2 or 3, wherein the mixture obtained in stage (I) is molded by extrusion pressing or extruding.
  5. A process as claimed in any of claims 2 to 4, wherein the molding containing a titanium silicalite has micropores, mesopores, macropores, micro- and mesopores, micro- and macropores or micro-, meso- and macropores.
  6. The use of the molding as claimed in claim 1 or of a molding produced by a process as claimed in any of claims 2 to 5 or of a mixture of two or more thereof for the epoxidation of organic compounds having at least one C-C double bond, for the hydroxylation of aromatic organic compounds, or for the conversion of alkanes to alcohols, ketones, aldehydes and acids.
  7. The use of the molding as claimed in claim 1 or of a molding produced by a process as claimed in any of claims 2 to 5 for the epoxidation of an olefin, preferably for the preparation of propylene oxide starting from propylene and hydrogen peroxide.
  8. The use of a mixture containing at least one alcohol and water as a pasting agent, in combination with a tetraalkoxysilane as a binder, for the preparation of a moldable mixture which contains a titanium silicalite.
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JP4921622B2 (en) 2012-04-25
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AU8336298A (en) 1998-12-21
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EP0991469B1 (en) 2002-02-27
US6491861B1 (en) 2002-12-10
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CA2293617A1 (en) 1998-12-10
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EP0991469A1 (en) 2000-04-12
ES2173599T3 (en) 2002-10-16

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